New bis



Patented Apr. 13, 1954 2,675,383

UNITED STATES PATENT OFFICE NEW BIS-(AMINOTRIAZINES) AND PROCESS FOR THEIR MANUFACTURE Peter L. de Benneville, Philadelphia, Pa., assignor to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application March 12, 1952, Serial No. 276,231

' 12 Claims. (Cl. 260-249-6) l1 2 1 This invention relates to a new class of bissecondary butylamine and Z-ethylhexylamine. (aminotriazines) and to their method of prepa- The Ca bo yl comp d RICORZ s d e 0116 ration. These new compounds have the general in which R1 is hydrogen or methyl and R2 is f rm l methyl, ethyl up to octyl. Representative carbonyl compounds are acetaldehyde, propionaldehyde, nonyl aldehyde, acetone and methyl ethyl ketone. Reactions (2) and (3) are both carried N- N out at room temperature or slightly above and in the case of reaction (3) an inert diluent such as l benzene should be used. f T Reaction (1), between the cyanoaminonitrile HaN-C\ /11NHi and dicyanodiamide, is carried out in an inert N solvent such as a lower alcohol and. in the presm which R is an alkyl group of one to eight cap ence or a small amount of alkaline catalyst such bon atoms having at least one hydrogen atom on 15 5 g 333 ggjg i gfi g gg g s if the carbon adjacent the nitrogen, R1 is hydrogen d n d b or methyl and R2 is an alkyl group of one to eight sig 11 z 23325.22 gg figg 1 is m 1 1 carbon atoms. They may be prepared by the t from the reaction medium as it is formed and is process represented'by the equatlon readily freed from excess dicyanodiamide by a (1) hot water wash.

1g. IE base The following examples illustrate the practice R N CN 2H N NHCN Of the invention.

1 EXAMPLE 1 i sm A. Preparation of- R1 N-G H t d t R-N -c N CH;N CN

5 Ha I N/ NH: A benzene solution of 34 parts of methylamine J'L is cooled to 5 C.'in a vessel equipped with a stirrer, a cooling jacket and an ice water condensing system. Forty-seven parts of acetalden Cop pp c serlal 276,232, hyde was added over a period of one-half hour filed March 12, 1952, it is shown that the cyano- 35 and then 29.5 parts of anhydrous hydrogen cyaaminonitriles, nid was added over a period of fifteen minutes. It; Stirring and cooling were maintained during & these additions, and thereafter the stirring was r continued for one hour while the reaction mix- N ture was allowed to come to room temperature. 1 of the class useful in the practice of this inven- It was allowed to stand overnight at room tem- E tion may be prepared by first forming an aminoperature. The benzene layer was then separated nitrile by the reaction anddistilled to yield 44 parts of water-White (2) aminonitrile boiling at 7078 C. at 34 mm.

1 R, R, 45 B. Preparation of- RNH1+$=O HON R-N-o-oN H2O H l 0H.-N--eoN and then reacting the aminonitrile with cyanogen CN B; chlorldfl accordmgtothe equation To a solution of the 44 parts of aminonitrile (3) as prepared in part A in 80 parts of benzene there R; R, was added first 16 parts of cyanogen chloride, R 1\II GN CXCN base H01 then 36.5 parts of anhydrous potassium carbonate (5 in 32 parts of water, and finally an additional 16.2 H N parts of cyanogen chloride. The solution was In reaction (2) the primary amine may be stirred during these additions and external coolmethylamine, ethylamlne, propylamine, isoing means applied. The rate of addition was propylamlne, normal butylamine. isobutylamine, adjusted to keep the temperature below 35 C.-

benzene layer. was then separated and distilledto yield 46 parts of the cyanoaminonitrile. (Distillation range 1l2-114 C./ 5 mm.)

C. Preparation of- W s r y of -8 parts of t a oa non trile prepared in part B 37 parts of dicyanodiamide, and 45 parts of isopropanol was heatedto reflux; ing temperature and to it was added over a period of ZO ninutes a hot solution of 6.6 par ts of poassiumhvd de 85 parts ef-i dn op nol.

I One hundred forty fou flparts of methyl. ethyl ketone containing one part of piperidine was p ced i a ionve selequ dwi ha ti and to it was added over a period of .45 minutes 108 parts of anhydrous hydrogen cyanide. During the addition the temperature of the mixture was in the range 25-45 C. Stirring was continued at room temperature for one and threequarter hours after all the hydrogen cyanide was added. The mixture was then acidified with 85 H3PO4 and stripped of excess hydrogen cyanide at C. and water pump vacuum. Fifty-six parts of hydrogen cyanide were removed. To the cy'anohydrin thus formed, there was added 62.8

parts of gaseous methylamine in one and threequarter hours at I -15 C. The resulting product distilled mainly at 75-77 C. at 28 mm. A 68 yield of aminonitrile was obtained as a colorless liquid.

B. Preparation of- To a solution of 117.5'parts of the ,aminonitrile as prepared in part A in 125 parts of benzene there was added a solutionof 64A parts of cyanogen chloride in 55 parts of benzene. The addition was made over a period of minutes during which the mixture was at a. temperature within the range 25-35 C. A solution of 69 parts of anhydrous potassium carbonatein '70 parts of water at a temperature of 207 25? C. was then added over a period of 15 minutes. The mixture was stirredfor one-half hour ,at. room temperature and '15 minutesat C. and then filteredto removepotassium chloride. The hen; zene layer was distilled and yieldedjl parts oi the 'cy'anoaminonitrile; a light yellow oil distill; 9 31 53 C" r v. t

C. Preparation of- I P on; NO l OHaN0-C N /0 :Ha N N I [5 H2NC -NH:

To a refluxing mixture of 41.1 parts of the cyanoaminonitrile of part B, 55.5 parts of dicyanodiamide, and 65 parts of isopropanol there 7 was added over a 35 minute period a solution of 9.9 parts of potassium hydroxide dissolved in 125 parts of isopropanol. The mixture was refluxed for 24 hours, cooled, filtered, and the filter residue washed with hot water and dried. Fifty and one-half parts of the bis-(aminotriazine) wasobtained. It is a colorless solid melting above 290 C.

EXAMPLE 3 A. Preparation ofn'--C4H9NCCN One hundred twenty and one-half parts of butylamine was placed in a reaction vessel equipped with stirrer and external cooling means. To this 106 .5 parts of lactonitrile was added over a period of one-half hour. The temperature of the mixture was within the range 2'7- 40 C. The reaction mixture was stirred forone hour at room temperature and then one-half hour at 50 C. Some water was present as a lower layer and more was separated by the addition of benzene. A total of 16.3 parts of water. was separated. The upper oil layer was distilled yielding 170.51 parts of aminonitrile. It is a pale yellow oil boiling at -97 C. at 31 mm.

B. Preparation ofriod of 25 minutes during which the temperature was v kept between -5 C. Stirring was continued for one and one-half hours at room temperature. The mixture was filtered and the benzene layer distilled. Ninety-seven and twotenths parts of cyanoaminonitrile was obtained as a very pale yellow oil boiling at 111-'112G. at

BITE:

l HaN- G Amixtureof 40 parts or isopropanol, 30.2 parts of the cyanoammonitrile prepared in part B and 37 parts of dicyanodiamide was heated torefluxing temperature (90 C.), and to it was added a solution of 6.6 parts of 85% potassium hydroxe ide in '19 parts of isopropanol. ,The mixture was stirred during the addition which was made in 10 minutes. Astrong exotherm developed during the addition and practicallyall the solid went into solution. After refluxing an additional five minutes, the reaction mixture solidified. To this 120 parts of isopropanol was added and the mixture heated for two hours at reflux (86). The solid was filtered and washed with hot water at 60 C. The washed residue was a tan solid melting at 179-180 C. It was extracted twice with hot methanol andyielded 31 parts of the purified bis-1 It is a colorless product melt- (aminotriazine) ing at 210-211 C.

EXAMPLE4 A. Preparation of- CH, Clix-li *GN H GHa Over a period of two hours 132.2 parts of gaseous monomethylamine was added to 340.4 parts ot-acetone cyanohy drin. During the addition, the temperature was kept in the range -10 C. to +10 C. The reaction mixture was then stripped at room temperature and used in part B without further purification.

B. Preparation of v (1H3 oer-w a -o N CN CH:

The crude aminonitrile as prepared in part A was mixed at C. with 352 parts of benzene, 276.8 parts of anhydrous potassium carbonate and 128 parts of water. There was then added, at -25 C. and over a period of minutes, 246 parts of cyanogen chloride. Stirring was continued for one-half hour at room temperature and the reaction mixture allowed to stand overnight. It was then heated to 5.0 C., cooled, the aqueous layer separated, and the benzene layer filtered, dried over anhydrousamagnesiuni sulfate and distilled. There was obtained 213.5 parts of a light brown oil boiling at 89-90 C. at 2 mm.

CLPreparation of- CHz-N-C 0 /N O OH: \NV=(|3 I I N I NH: HzN-C ..E-NH2- To a stirred mixture of 200 parts of isopropanol, 128.2 parts of the cyanoaminonitrile as prepared in part B, and 193 parts of dicyanodiamide there was added toreflux (-85' C.) and over a period of 90 minutes a solution of 35 parts of potassium hydroxide in 400 parts of isopropanol. The mixture was stirred at reflux for 2.5 hours and then cooled. The fine white solid which had formed was filtered offend washed with temperature and then "for 30 minutes at 50 C.

E; part B, and 25.9 parts of dicyanodiamide there hot water.

at430-435 C.

7 EXAMPLE 5, A. Preparation-of-- UH! C4H9-N-CN Over a. period of 15 minutes and at a temperature of 25-40 (2., 127.4. parts of acetone cyanohydrin was added to 120.5 parts of n-butylamine. Stirring was continued for '75 minutes at room The reaction mixture was cooled to room temperature and :benzene added. Seventeen parts of water was separated. The benzene layer was distilled and yielded v182 parts of aminonitrile as ape-1e yellow liquid boiling at 86- 88 C. at 28 B. Preparation of C Carrie-(LON N CH:

To a stirred solution of 44 parts of benzene and 30.8 parts of cyanogen chloride there was added ta solution of 71.3 parts of aminonitrile prepared was obtained as a pale yellow liquid boiling at .96

C. atl mm. 7 I i 0. Preparation of- NHQ To a stirred mixture of 44 parts of isopropanol, 23.2 parts of cyanoaminonitrile as prepared in was added at reflux (85;C.) a solution of 4.6 parts of 85% potassium hydroxide in 56 parts of isopropanol. The addition was made over a period of 15 minutes'by which time all ingredients were in solution. Heating at reflux was COD". tin-tied and after 30 minutessome solid precipitated. The refluxing was continued for an addi tional six hours and the reaction mixture was then cooled, filtered and washed with hot water.

= zTwenty-two parts of bls-triazine, a white solid melting at 271-272 C., was obtained.

A. Preparation of Ga as-e es H sH-n ii a. was is fit-ma eraea-trimahs-l Two hundred twentyesix parts of 'f the Ibis-(aminotriazine) was obtained. It melted hexaldehyde cyanohydrin and 40 parts of benzene r B. Preparation of- A solution of 98.6 parts of the above aminoaminonitrile boiling at 133-140 C. at 1.5 mm.

C. Preparation of- To a mixture of 38.6 parts of the cyanoaminonitrile of part B, 40 parts of isopropanol, and 37 parts of dicyanodiamide there was quite rapidly added at 85 C. a solution of 6.6 parts of potassium hydroxide, reagent grade, in 80 parts of isopropanol. The mixture was refluxed for 22 hours, filtered at room temperature, and the residue Washed with hot water (65 C.) On air-drying, there was obtained 40 parts of solid product melting at 256-258 C.

EXAMPLE 7 A. Preparation of- OaHn-Jf- -ON I H Hg To 68 parts of 2-ethylhexylamine there was I added rapidly at 25-45 (2., with cooling, 59.5

parts of acetone cyanohydrin. After the mixture was stirred one hour it was stripped to yield 96 parts of the aminonitrile.

B. Preparation of-'- A suspension was formed by stirring 39 parts of the aminonitrile of part A, 40 parts of benzene, and 14.5 parts of anhydrous potassium carbonate in parts of water. Into this suspension was passed 13.6 parts of cyanogen chloride gas over a period of 20 minutes. The water layer was To this mixture was then added at I off g separated, and the benzene layer dried and distilled. Ten parts of the cyanoaminonitrile boiling at 136-146 C. at 4.5 mm. were obtained.

0. Preparation of- To a mixture of 8 parts of the cyanoaminonitrile of part B, 8.4 parts of dicyanodiamide and 40 parts of isopropanol there was added at reflux a solution of two parts of potassium hydroxide in I 35 parts of isopropanol. After refluxing for 12 hours, the mixture was cooled, filtered and the filtrate washed with hot water at C. Six

parts of dried bis-(aminotriazine) melting at 243-246 C. was obtained.

The bis-(aminotriazines) of the class herein described combine with formaldehyde or formaldehyde and an alcohol to yield useful resinous condensation products. Such products are described in copending application Serial No. 276,233, filed on even date herewith, now Patent No. 2,653,143.

I claim:

1. As new compositions of matter, the bis- (amino triazines) having the formula HnN-) wherein R is an alkyl group of one to eight carbon atoms having at least one hydrogen atomon the carbon atom adjacent to the nitrogen atom,

R1 is selected from the group consisting of H and CH3 and R2 is an alkyl group of one to eight 3. As a new composition of matter, the his- (aminotriazine) having the formula 4. As a new composition of matter, the his- (aminotriazine) having the formula 5. The process which comprises reacting under alkaline conditions dicyanodiamide and a cyanoaminonitrile of the formula wherein R is an alkyl group of one to eight carbon atom having at least one hydrogen atom on the carbon atom adjacent to the nitrogen atom, R1 is selected from the group H and CH3 and R2 is an alkyl group of one to eight carbon atoms.

6. The process which comprises reacting under alkaline conditions dicyanodiamide and a. cyanoaminonitrile of the formula 7. The process which comprises reacting under alkaline conditions dicyanodiamide and a cyanoaminonitrile of the formula 8. The process which comprises reacting under alkaline conditions dicyanodiamide and a cyanoaminonitrile of the formula 9. As a new composition of matter, the bis- (aminotriazine) having the formula 10. As a new composition of matter, the his- (aminotriazine) having the formula References Cited in the file of this: patent UNITED STATES PATENTS 40 Number Name Date 2,459,397 Thurston Jan. 18, 1949 2,532,519 Simons Dec. 5, 1950 2,606,904 Kaiser Aug. 12, 1952 

1. AS NEW COMPOSITION OF MATTER, THE BIS(AMINO TRIAZINES) HAVING THE FORMULA 